Synthesis of pyrazole derivatives and their evaluation as photosynthetic electron transport inhibitors

Two series of new pyrazoles, namely six pyrazolo[1,5-a][1,3,5]triazine-2,4-dione and four pyrazolo[1,5-c][1,3,5]thiadiazine-2-one derivatives, were synthesized as potential inhibitors of the photosynthetic electron transport chain at the photosystem II level. The compounds were confirmed by 1H NMR, elemental, and IR analyses. Their biological activity was evaluated in vivo upon both the growth of blue-green algae and the photosynthetic oxygen evolution by eukaryotic algae and in vitro as the ability to interfere with light-driven reduction of ferricyanide by isolated spinach chloroplasts. Some compounds exhibited remarkable inhibitory properties, comparable to those of the reference commercial herbicides lenacil, diuron, and hexazinone. Results suggest that the substitution of triazine with thiadiazine ring may act as amplifier for herbicidal activity.     

Synthesis and fungistatic activity of new groups of 2,4-dihydroxythiobenzoyl derivatives against phytopathogenic fungi

Twenty-six compounds, derivatives of amides, hydrazines, hydrazides, hydrazones, and semicarbazides, with a 2,4-dihydroxythiobenzoyl moiety, were synthesized from sulfinyl-bis(2,4-dihydroxythiobenzoyl). The compositions and chemical structures of these compounds were confirmed by IR, (1)H NMR, EI-MS, and elemental analysis. Antifungal properties of chemicals under in vitro conditions against five phytopathogenic fungi were estimated. In vivo studies against Erisiphe graminis were also carried out. The compounds N-substituted with an 2,4-dihydroxythiobenzamide group proved to be the most active. N-2-(1-Cinnamylbenzene ester)-2,4-dihydroxythiobenzamide, under in vitro conditions, showed activity at the level of 80-100% development of most pathogens at a concentration of 20 microg/mL and partially at a concentration of 200 microg/mL. For compounds with -HN-NH- or -NH-N= moiety, weak or no fungistatic properties were found at the concentrations studied.     

Some furfural derivatives as nitrification inhibitors

Three series of furfural derivatives, namely N-O-furfural oxime ethers, furfural Schiff bases (furfurylidene anilines), and furfural chalcones, have been synthesized and evaluated for nitrification inhibition activity in laboratory incubation studies in typic Ustocrept soil. Furfural oxime ethers and furfural Schiff bases showed potential activity, but furfural chalcones were only mildly active. N-O-ethyl furfural oxime among the oxime ethers, and furfurylidine-4-chloroaniline among the furfural Schiff bases, performed the best. These two compounds showed more than 50% nitrification inhibition on the 45th day at 5% dose as compared to 73% inhibition by nitrapyrin. Activity of furfural oxime ethers decreased with an increase in carbon atoms in the N-O-alkyl side chain. Introduction of a chlorine atom in the phenyl ring of furfurylidene anilines increased the persistence of their activity. N-O-Ethyl furfural oxime and furfurylidine-4-chloroaniline coated urea performed at par with their application in solution form. Ethyl and N-O-isopropyl oxime, as well as chloro- and nitro- substituted Schiff bases, did not reveal any phytotoxicity (adverse effect on germination) on chickpea seeds (Cicer arietinum) even at the highest dose (40 ppm, soil basis).     

Evaluation of some phosphoroamides as soil urease inhibitors

Summary The effectiveness of six phosphoroamides for retardation of urea hydrolysis in soils was studied by determining the effects of 10 g g^–1 soil of each compound on the amounts of urea hydrolyzed when soils treated with urea were incubated at 10°, 20°, 30°, and 40°C for 3, 7, and 14 days. The phosphoroamides used wereN-(diaminophosphinyl)-cyclohexylamine,N-benzyl-N-methyl phosphoric triamide, diethyl phosphoric triamide, trichloroethyl phosphorodiamidate, dimethyl phosphoric triamide, andN-butyl phosphorothioic triamide [N-(n-butyl) thiophosphoric triamide]. The soils used were selected to obtain a range in properties, and the effects of the six phosphoroamides studied were compared with those of two compounds known to be among the most effective compounds thus far proposed for retardation of urea hydrolysis in soils (phenylphosphorodiamidate and hydroquinone). The data obtained showed that all six of the phosphoroamides evaluated compared favorably with hydroquinone as soil urease inhibitors and that two of them [N-butyl phosphorothioic triamide andN-(diaminophosphinyl)-cyclohexylamine] were superior to phenylphosphorodiamidate for retardation of urea hydrolysis in soils at 20°, 30°, or 40°C.     

Synthesis and antiviral activities of pyrazole derivatives containing an oxime moiety

Target compounds 4a- n were obtained by the reaction of 1-substituted phenyl-3-methyl-5-substituted phenylthio-4-pyrazolaldoximes (3) with chloromethylated heterocyclic compounds (ClCH 2-R 3) under reflux conditions in ethanol. Subsequently, the oxidation of 4a- e with KMnO 4 in HOAc at room temperature afforded eight new compounds, 5a- h. The synthesized compounds were characterized by physical constants, and the structures of the title compounds were confirmed by IR, (1)H NMR, (13)C NMR, and elemental analysis. The bioassay revealed that the compounds possessed antiviral activities. It was found that title compounds 4a and 4g had the same inactivation effects against TMV (EC 50 = 58.7 and 65.3 microg/mL) as the commercial product Ningnanmycin (EC 50 = 52.7 microg/mL). To the best of our knowledge, this is the first report on the antiviral activity of pyrazole derivatives containing an oxime moiety.     

镉胁迫导致番茄根际富集病原菌黄瓜织球壳菌

植物根际真菌群落与植物的健康紧密相关,且我国农田土壤重金属镉(Cd)污染严重,因此,探究Cd 胁迫对农作物根际真菌群落的影响具有重要的现实意义。通过盆栽试验,采用Illumina 高通量测序技术研究Cd 胁迫对番茄根际土壤真菌群落的影响。结果表明,Cd 胁迫明显改变了番茄根际土壤真菌的组成和结构,显著降低了Chao和ACE 指数,增加了子囊菌门(Ascomycota)、壶菌门(Chytridiomycota)和毛霉门(Mucoromycota)等优势菌门的丰度。Spearman 相关性分析表明,Cd 胁迫会导致“萎蔫病”的致病真菌黄瓜织球壳菌(Plectosphaerella cucumerina)的显著富集。为了验证富集真菌的致病性,分离黄瓜织球壳菌的纯培养(菌株命名:R-2)。水培试验表明,R-2 显著降低了番茄幼苗的株高(21.43%)、根长(46.99%)和鲜重(34.79%),验证了R-2 是植物病原菌。总体而言,发现Cd 胁迫会导致番茄根际富集植物病原真菌这一现象,可为中、轻度Cd 污染农田土壤的安全生产提供科学依据。     

Structural characteristics of phosphoramide derivatives as urease inhibitors. Requirements for activity

Taking as a reference the structural characteristics of a set of compounds that act as jack bean ( Canavalia ensiformis) urease inhibitors, namely, phenylphosphorodiamidate (PPD), N- n-butylthiophosphorictriamide (NBPT), and N- n-butylphosphorictriamide (NBPTO), we have studied the structure-activity relationships of a series of phosphoramide derivatives for which the activity as urease inhibitors in both in vitro and in vivo assays is known. Molecular modeling studies were carried out, and the results highlighted the relevance of characteristics such as the presence of intramolecular hydrogen bonds, the volume of the fragment involved in the enzyme interaction, and the degree of conformational freedom as well as the HOMO orbital and atomic orbital contributions to the HOMO orbital, electron density, and PEM distributions on the activity of these compounds as urease inhibitors. These data, along with the preliminary docking study carried out, allow us to propose a union mode to the active site of the enzyme for these compounds.     

Fungicidal property of Curcuma longa L. rhizome-derived curcumin against phytopathogenic fungi in a greenhouse

Fungicidal activity of Curcuma longa rhizome-derived materials against Botrytis cineria, Erysiphe graminis, Phytophthora infestans, Puccinia recondita, Pyricularia oryzae, and Rhizoctonia solani was tested using a whole plant method in vivo. It was compared with synthetic fungicides and four commercially available compounds derived from C. longa. The response varied with the tested plant pathogen. At 1000 mg/L, the hexane extract of C. longa showed fungicidal activities against E.graminis, P. infestans, and R. solani, and the ethyl acetate extract of C. longa showed fungicidal activities against B. cineria, P. infestans, Pu. recondita, and R. solani. Curcumin was isolated from the ethyl acetate fraction using chromatographic techniques and showed fungicidal activities against P. infestans, Pu. recondita, and R. solani with 100, 100, and 63% control values at 500 mg/L and 85, 76, and 45% control values at 250 mg/L, respectively. In the test with components derived from C. longa, turmerone exhibited weak activity against E. graminis, but no activity was observed from treatments with borneol, 1,8-cineole, sabinene, and turmerone. In comparison, potent fungicidal activity with chlorothalonil against P. infestans at 50 mg/L and dichlofluanid against B. cinerea at 50 mg/L was exhibited. These results may be an indication of at least one of the fungicidal actions of curcumin derived from C. longa.     

Antimycotic activities of selected plant flora,growing wild in Lebanon,against phytopathogenic fungi

Petroleum ether (PE) and methanolic extracts of nine wild plant species were tested in vitro for their antimycotic activity against eight phytopathogenic fungi. The efficacy of PE extracts against all pathogens tested was higher than that of methanolic extracts. Wild marjoram (Origanum syriacum) PE extract showed the highest and widest range of activity. It resulted in complete inhibition of mycelial growth of six of eight fungi tested and also gave nearly complete inhibition of spore germination of the six fungi included in the assay, namely, Botrytis cinerea, Alternaria solani, Penicillium sp., Cladosporium sp., Fusarium oxysporum f. sp. melonis, and Verticillium dahlia. The other plant extracts showed differential activities in the spore germination test, but none was highly active against mycelial growth. Inula viscosa and Mentha longifolia were highly effective (>88%) in spore germination tests against five of six fungi tested, whereas Centaurea pallescens, Cichorium intybus, Eryngium creticum, Salvia fruticosa, and Melia azedarach showed >95% inhibition of spore germination in at least two fungi. Foeniculum vulgare showed the least antimycotic activity. Fractionation followed by autobiography on TLC plates using Cladosporium sp. as a test organism showed that O. syriacum PE extracts contained three inhibition zones, and those of Inula viscosa and Cichorium intybus, two, whereas the PE extracts of the remaining plants showed each one inhibition zone. Some of the major compounds present in these inhibition zones were identified by GC-MS. The possibility for using these extracts, or their mixtures, to control plant diseases is discussed.     

Effect of salinity and arbuscular mycorrhizal fungi on growth and some physiological parameters of Citrus jambheri

Arbuscular mycorrhizal (AM) fungi alleviate the unfavorable effects of salinity stress on plant growth. A pot study was conducted to determine the effects of AM fungi and salt on growth and some physiological parameters of Citrus jambheri rootstock. Four levels of salinity (2, 4, 6, and 8 dS m^?1 as NaCl) and three mycorrhizal treatments (Glomus etunicatum, Glomus intraradices and non-mycorrhizal (NM) control) were used. As salinity increased, all measured characteristics of plants after 4.5-month growth except Na uptake, proline content, and electrolyte leakage decreased. Shoot dry weight and K uptake were significantly higher in G. intraradices-colonized seedlings than NM controls at all salinity levels. Root dry weight and shoot P uptake were significantly higher in G. etunicatum-colonized seedlings than NM controls at all salinity levels. G. intraradices-colonized seedlings had significantly higher proline content than NM controls and G. etunicatum-colonized seedlings at salinity levels of 4, 6 and 8 dS m^?1. The electrolyte leakage percentage was significantly lower in G. intraradices-colonized seedlings than NM controls at all salinity levels. The data demonstrated that mycorrhizal citrus seedlings exhibited greater tolerance to salt stress than NM seedlings and the enhanced proline content seems to be one of the mechanisms involved.     

三种吡唑类硝化抑制剂在潮棕壤中的垂直和水平迁移

分别利用土柱淋溶试验和水平扩散试验研究了3种吡唑类硝化抑制剂[3-甲基吡唑(MP)、3,4-二甲基吡唑磷酸盐(DMPP)和4-氯-3-甲基吡唑(ClMP)]随水在潮棕壤中垂直和水平迁移及与NH4+移动的同步性。结果表明,淋溶试验结束后(总淋洗量700 mm),各土层(0、10、20 cm)MP含量与NH4+-N含量的比值未发生变化,而DMPP和ClMP含量与NH4+-N含量的比值随土层深度增加显著降低。扩散试验结束后,在距圆心40 mm范围内,MP和DMPP含量与NH4+-N含量的比值均未发生较大变化,而ClMP含量与NH4+-N含量比值显著减小。研究结果说明,MP随水沿垂直和水平方向移动的速率几乎和NH4+一样,不存在同NH4+脱离风险,而DMPP和ClMP随水移动的速率比NH4+慢。     

Design, synthesis, and biological evaluation of phosphoramide derivatives as urease inhibitors

The design, synthesis, and biological evaluation of phosphoramide derivatives as urease inhibitors to reduce the loss of ammonia has been carried out. Forty phosphorus derivatives were synthesized and their inhibitory activities evaluated against that of jack bean urease. In addition, in vivo assays have been carried out. All of the compounds were characterized by IR, (1)H NMR, MS, and elemental microanalysis. In some cases, detailed molecular modeling studies were carried out, and these highlighted the interaction between the enzyme active center and the compounds and also the characteristics related to their activity as urease inhibitors. According to the IC(50) values for in vitro inhibitory activity, 12 compounds showed values below 1 microM and 8 of them represent improvements of activity in comparison to the commercial urease inhibitor N-n-butylthiophosphorictriamide (NBPT) (100 nM) (AGROTAIN). On the basis of the activity results and the conclusions of the molecular modeling study, a structural model for new potential inhibitors has been defined.     

Pyrazole derivatives as photosynthetic electron transport inhibitors: new leads and structure-activity relationship

Four series of new pyrazoles, namely, 5 4-carboxypyrazolo-3-tert-butylcarboxamide and 6 4-carboxypyrazolo-3-cyclopropylcarboxamide derivatives and 10 pyrazolo[3,4-d][1,3]thiazine-4-one and 9 pyrazolo[3,4-d][1,3]thiazine-4-thione derivatives, were synthesized and screened as potential inhibitors of photosynthetic electron transport. The structures were confirmed by 1H NMR, elemental, and IR analyses. Their biological activity was evaluated in vitro as the ability to interfere with the light-driven reduction of ferricyanide by isolated spinach chloroplasts. Only a few compounds exhibited excellent inhibitory properties in the micromolar range, comparable to those of commercial herbicides sharing the same target, such as diuron, lenacil, and hexazinone. Nevertheless, most of the remaining molecules exerted a remarkable inhibition in the millimolar range. Combined with previous results on 6 pyrazolo[1,5-a][1,3,5]triazine-2,4-dione and 4 pyrazolo[1,5-c][1,3,5]thiadiazine-2-one derivatives, these data allowed a comprehensive analysis of structure-activity relationship. Molecular modeling studies were undertaken to rationalize the structural determinants of activity in terms of shape, size, and molecular fields. Results suggested that the inhibitory potential of these compounds is associated mainly with their electrostatic properties.     

Grazing preferences of some collembola for endomycorrhizal fungi

The ability of five collembolan species to distinguish and graze selectively on vesicular-arbuscular mycorrhiza (VAM) has been verified. Four species preferred the food infected by VAM fungi. All collembolan species showed more of less significant preferences for one species/isolate of the VAM fungi.     

Synthesis and insecticidal activity of novel carbamate derivatives as potential dual-binding site acetylcholinesterase inhibitors

In biological systems, bivalent ligands often possess increased functional affinity for their receptors compared with monovalent ligands. On the basis of the structure of acetylcholinesterase (AChE), a series of novel carbamate heterodimetic derivatives were designed and synthesized with the aim of increasing the potency toward AChE inhibition. The AChE inhibitory ability of all the novel compounds was tested using AChE obtained from the brain of the housefly. The bioassay results showed that compounds 6j, 6k, 6m, 6n, 6p, and 6q had increased inhibitory activities in comparison with parent phenyl N-methylcarbamate (MH) at the concentration of 100 mg/L. Among them, the most potent AChE inhibitor of these compounds was 6q (IC(50) = 12 μM), which showed 62-fold greater AChE inhibitory activity than that of MH and 12-fold greater activity than metolcarb (MT), which suggested that the 3-nitrophenoxy moiety of compound 6q was able to interact with the aromatic amino acid residues lining the gorge and the phenyl N-methylcarbamate moiety was able to interact with the catalytic sites of AChE, simultaneously. The insecticidal activities of compounds 6j, 6k, 6m, 6n, 6p, and 6q were further evaluated. Consistent with the result in vitro bioassay, those compounds demonstrated better activities against Lipaphis erysimi than parent compound MH at the concentration of 300 mg/L, and compound 6q showed the best insecticidal activity, causing 98% mortality after 24 h of treatment.     

Effect of SO2 and NH3 on growth behavior of some phylloplane fungi of wheat in in vitro

The colony growth of some phylloplane fungi of wheat viz. Alternaria alternata, Aspergillus favus, Amiger, Cladosportium cladosporioides, Curvularia lunata, Drechslera australiensis, Epicoccum purpurascens, Fusarium oxysporum, Penicillium chrysogenum and P. citrinum were studied in chamber fumigation experiments exposed to 2669 ± 105 μg SO₂ m^?3 and 708.33 ± 55 μg NH3 m^?3 air, separately, for 10, 30 and 60 min. The colony growth of all the test fungi was significantly (P=0.01/0.005) inhibited on prolonged period of SO₂/NH₃ exposure. However, some of the test fungi namely A. favus, A. niger, E. purpurascens and F. oxysporum showed growth stimulation after 10 min exposure of SO₂. Similarly, the growth of C. lunata and F. oxysporum increased only after 10 min exposure of NH3. The inhibitory effect of SO₂/NH₃ was directly correlated with the exposure times.     

Antifungal effects of different organic extracts from Melia azedarach L. on phytopathogenic fungi and their isolated active components

Extracts from different parts of Melia azedarach L. were studied as potential antifungal agents for selected phytopathogenic fungi. In a serial agar dilution method, hexanic and ethanolic extracts from fruit, seed kernels, and senescent leaves exhibited fungistatic activity against Aspergillus flavus,Diaporthe phaseolorum var. meridionales, Fusarium oxysporum, Fusarium solani, Fusarium verticillioides, and Sclerotinia sclerotiorum. Both hexanic extract from senescent leaves and ethanolic extract from seed kernel were highly effective on all tested fungi, with minimum inhibitory concentration (MIC) values ranging from 0.5 to 25 mg/mL and 0.5 to 5 mg/mL, respectively. In addition, all of the above-mentioned extracts showed fungicidal activity on these fungi, with ethanolic seed kernel extract being the most active. Three compounds displaying activity against F. verticillioides were isolated from the ethanolic seed kernel extract and were characterized as vanillin (1), 4-hydroxy-3-methoxycinnamaldehyde (2), and (+/-)-pinoresinol (3), with MICs of 0.6, 0.4, and 1.0 mg/mL, respectively. These compounds also showed a synergistic effect when combined in different concentrations, needing four times less concentration to reach complete inhibition in the growth of F. verticillioides.     

Synthesis and biological activities of novel pyrazole oxime derivatives containing a 2-chloro-5-thiazolyl moiety

A series of novel pyrazole oxime derivatives containing a 2-chloro-5-thiazolyl moiety were synthesized. Their structures were confirmed by (1)H NMR, (13)C NMR, and elemental analysis. The preliminary bioassays showed that all of the title compounds had low acaricidal activity against Tetranychus cinnabarinus . However, most of them exhibited excellent insecticidal activity against Aphis medicagini at the dosage of 0.5 mg/mL, and some compounds still showed good insecticidal activity against A. medicagini even at the dosage of 0.2 mg/mL. Meanwhile, some title compounds displayed fungicidal and plant growth regulatory activities.